Dimethyl and di-n-butyl esters of itaconic acid were polymerized and their glass transition temperatures along with those of copolymers obtained with the mentioned ester of itaconic acid with methyl methacrylate have been studied by differential scanning calorimetry. Homopolymer glass transitions decreased as the chain length of ester alkyl groups increased. The glass transition temperatures of copolymer have been analysed as a function of the sequence distribution and their values compared to the theoretical ones derived using Johnson’s equation. The values for the supposed transition temperature of the alternating copolymers, T-g12, are lower than the averages values expected from the additive contribution of the T-g of the corresponding homopolymers and decreases as the itaconic diester chain lengthens. Comparison of these polymers with the corresponding poly(n-alkyl acrylate)s and their copolymers with methyl methacrylate highlighted the similarities in properties.